Non-electrostatic resin molding composition containing hydroxyalkylated polyethylenepolyamine



United States Patent 2,891,030 NON-ELECTROSTATIC RESIN MOLDING COMPO- SITI ON CONTAINING HYDROXYALKYLATED 5 AMINE,

POLYETHYLENE POLY Myron A. Coler, Scarsdale, andAmoldS. Louis, Riverdale, N .Y.

N0 Drawing. Application March 30, 1956 Serial No. 574,951

Claims. (Cl. 260-32.6)

Thisinvention relates to improved synthetic resin mold! 1 ingcompositions and, in particular, to such molding materials which avoid the highly undesirable effects of elec- This application is a continuation-in-part of our copending application entitled Non-Electrostatic Molding Compositions, Serial Number 556,401, filed December synthetic resins causes the generation of high electrostatic charges. This evidences itself frequently by the formation of crows feet, fern-like and zig-zag patterns through the attraction of fine dust particles from the atmosphere. Such patterns are sometimes erroneously interpreted as being molding flaws.

The literature discloses many additives for rendering synthetic resins destaticized. Many of such additives depend on t e property of deliquescence to cause the article ceptible to electrostatic charging during the molding operation or upon release from the mold.

This invention does not depend on deliquescent action and, ltherefore, produces results substantially independent of humidity. This advantage of this invention is important in the elimination of the tendency for dust patterns to form on freshly molded plastic articles. Wehave found that certain hydroxyalkylated polyethy-lene polyamines when incorporated intosynthetic resin molding compositions renders the composition incapable 6 of generating or maintaining electrostatic charges.

A totally unexpected advantage of the above named proved tfiOW properties of the base plastic so as to permit shorter molding cycles aswell as improved filling 2,891,030 Patented June 16,,

2 of thin mold sections; reduced breakage of, moldings and easier mold release were obtained.

An object of this invention is, therefore, to provide; a, method for eliminating the formation of electrostatic: charges on molded plastic articles.

Another object is to provide a plastic moldingcompbsiztion having improved molding properties.

Still another object is to provide a plastic. molding composition having preferred flow properties. when. in-' jection molded. t

A particular object is to provide a plastic material. which is substantially non-susceptible to acquiring electrostatic charges.

A particular object of this invention is, to... provide .a method for eliminating the formation of electrostatic charges on molded plastic articles during and especially immediately after the molding operation.

Another object is to provide articles comprising polystyrene compositions which are free of the effects of electrostatic charges.

Still another object of this invention is to. provide an improved plastic composition and methods of making same.

A still different object is to reduce the electrostatic charge on polystyrene objects made by injection moldings.

the following. detailed description proceeds:

The hydroxyalkylated polyethylene polyamines, having from 2 to 4 ethylene groups, employed in the compositions of this invention are characterized by the following formulas:

R ER nun R/ H Th R H III R Pentahydroxyalkylated diethylene triamine;

R H H H H H E R R lllllllll R Hexahydroxyalkylated tliethylene tetramine;

R H H H H H H H H R wherein R is a hydroxyalkyl radical containing from ,2 to 8 carbon atoms.

While we have shown the preferred form, namely the totally hydroxyalkylated compounds, it is to be under symbol R, need not the alike but may differ in al given compound. Mixtures of the above described mate rials may be employed within the total limits given hereinafter. t t l It iswithin the scope of this invention to employ ,as additives for synthetic resin molding compositions the 5 acid salts produced by reacting hydroxyalkylated poly:

ethylene polyamines with acids. Likewise e may employ the quaternary ammonium salts produced by reacting alkyl or alkyl aryl salts and alkyl or alkyl aryl halides with hydroxyalkylated polyethylene polyamines.

It has been discovered in the course of experimentation with materials of the type described ,abovethat certain polyamines substituted with short chain hydroxy alkyl groups in the N-position tend to cause pulling or the formation of blowholes during extrusion or molding. The permissible chain length is dependent on the degree of substitution in a manner which cannot be simply stated except to say that longer chains are excluded as the degree of substitution is decreased. The situation is adequately covcred if only these additives having a vapor pressure less than 760 mm. at 225 C. are used. If more volatile compounds are used, gassing during extrusion or molding becomesobjectionable.

By incorporating any of the above mentioned additive's or mixtures thereof in polystyrene or other resinous polymers the destatic zing properties areattained without incurring any of the undesirable features enumerated above. The quantity of additive employed is between 1- and 7% :by weight based on the total product and preferably between 2 and 6%. The upper limit is a matter of choicedictated by considerations of economy and is not critical. For example 10% or more may be used and the desired destaticizing results obtained, although at higher concentrations there is danger of atfecting physical properties adversely.

' While additives having the above described tendency are obviously not desirable in compositions which are to be molded or extruded at high temperatures, it has been found that such materials can be used to make up a minor proportion of the total addition when used in company with preferred additives.

Be it observed that it will often be advantageous to prepare a master batch of resin with incorporated additive, said master batch containing far more additive than is recommended for use in molding operations and being later cut back by extrusion or by being otherwise blended with untreated resin. Such a concentrate may well be sold, particularly in the clear or natural color for blending with untreated resin of various colors or of its own color. The master batch may contain up to 50% of the additive.

By way of illustration, there are given hereinafter a number of examples wherein the additive, quantity of additive and the resinous polymer employed are varied. Since hundreds of combinations are possible, it becomes impractical to show more than a few typical composi tions with additives so selected from the described group as to show operability of the group as a whole and therefore, such examples shall not be regarded as limiting in any sense.

Where it is desired to prepare a master batch or to market a concentrated blending material, the procedures of Examples 13 and are preferred. In plants where mass polymerization is employed, the procedures of Examples 14 and 15 will be especially useful.

In cases where plastic chip is to be treated or where the polymerization methods in use are not adapted to taking advantage of the processes mentioned above, the process of Example 7 is preferred for its simplicity and freedom from extra drying steps.

HWhere it is desired to incorporate pigment in the plastic as well as to render it antistatic, the processes of Examples 1 and 2 are preferred. This procedure is claimed in our copending application entitled Process for Making Plastic Compositions, Serial Number 532,- 132, filed September 2, 1955.

In carrying out this last referred to process, the additive is dissolved in a solvent which is a non-solvent for theplasticsemployed. The solution and plastic in comminuted form are then mixed together. The solvent is then removed so as to deposit the additive over the plastic particles.

' In accordance with a particular example of this last mentioned procedure, from 0.1 to 0.7 pound of the additives. are dissolved in 1 pound of isopropyl alcohol. 'Sutficient comminuted resinous polymer to make a total 'of 10 pounds of additive plus polymer is mixed with the suitable temperature for molding press with solution. The alcohol is then evaporated in an exhaust oven at 65 C. for 36 hours with occasional agitation, so as to leave the polymer granules uniformly coated with said additive.

The coated material is then fed through a Windsor type RC-65 twinscrew extruder equipped with a series of A3" square orifices. The die and barrel are maintained at a the particular polymer, such as 400 F. for polystyrene. The extruded material may then be chopped up into molding granules.

The molding granules may then be injection molded, as for example on a' Reed-Prentice 8-ounce injection a heater temperature of 600 F. for polystyrene. 'For other polymers conventional molding temperatures prescribed by the polymer supplier may be employed. i

As a test of the efiectiveness of the additive the resulting articles may be promptly sprayed with fine. bentonite dust by means of a hand sprayer. The dust will collect in patterns on charged areas. Additional moldings may be set aside and observed periodically for several weeks. Using a Keithley electrostatic voltmeter, the

, potential may be measured between the molding and ground immediately after withdrawal from the mold.

As a control means, identical articles may be molded from the same polymer not using the additive.

Example 1 Polystyrene granules, 10-60 mesh (Monsanto chemical Corp., L2020 PIX-6) 9 7 The dust test showed the absence of charged areas. The electrostatic voltmeter reading was about 1 volt.

One control article was sprayed with the bentonite dust immediately after molding and a well defined fern-like" pattern was immediately apparent. The same control article yielded a 20 volt reading on the electrostatic volt-' meter upon removal from the mold. After long term storage, another unmodified polystyrene molding showed definite dust patterns whereas the modified polystyrene article showed but a few isolated gravity deposited grains.

The molding characteristics of the modified polystyrene were judged to be superior to that of the control or 1111'. modified polystyrene by the molding machine operator on the basis of obviously improved ease of mold release and lower breakage of thin-walled moldings.

Example 2 Example 3 Example 1 was repeated with the same additive in a concentration of 1% by weight of the total product. The resulting molding exhibited poor non-electrostatic properties, as measured by the Keithley voltmeter.- A small amount of dust was collected in patterns after storage for two weeks. a

7 Example 3 Example 1 was repeated using 0.6 lb. of the same additive and 9.4 lbs. of polystyrene. A slight improvement in destaticizing properties was noted.

droxypropylateddiethylene: triamine. were mixed 1 together to form asolution of! watery consistency. The; foregoingmixture was worked in a sigma blade mixer. with. 9.4 lbs. ofipnlystyrene. After 15 minutes the particles were found toplie coatedwithi thetadditive; The coated. particleswere then dried at 65 C. for 24 hours to.rernovethe alcohol.

Theteoated particleswere thenxput throughthe extruder, chopped and molded as in Example 1 The resulting products showed substantially thesame properties as the modifiedi compositions oft Example 1. t

Example 7 0.6- pound of septahydroxypropylated tetraethylene pentamine ethyl ammoniumchloride and 9.4 pounds of polystyrenegranules as used in Example 1 werethoroughly. mixed in a* sigma blade mixer. The "mixture was then extruded; chopped andmoldedas in Example 1 The molded articles showed no discernable electrostatic charge as measured" on theKeithley-meter. The molded articlesshowed no tendency to collect dust in patterns during a 30-day storage test.

Example 8.

Example 1 was repeated using as the additive pentaliydroxybutylated dietliylene triamine. comparable;

' Example 9 i The procedure of Example 7 was repeated using,9.4 lbs. of a so-called high impact polystyrene which was a plastic alloy of 85% polystyrene, polybutadiene, 10% polyacrylonitrile and 0.6 pound of hexahydroxypropylated triethylene tetramine.

The molded product was compared with a control specimen prepared in identical fashion with the exception that the additive was omitted. The two specimens were opaque in appearance. Immediately after molding, the treated material showed a charge of one volt whereas the unmodified control showed a charge of 18 volts.

Example 10 The procedure of Example 7 was repeated using 0.6 lb. of hexahydroxyethylated triethylene tetramine, 9.4- lbs. of polyvinyl chloride and a barrel and die temperature of 390 F. Injection molding was carried out at 400 F. The resulting molded articles were similar in appearance to unmodified polyvinylchloride and exhibited excellent molding and anti-static properties. The electrostatic voltmeter test yielded a reading of about 1.8 volts whereas untreated polyvinylchloride showed a reading of 20 volts upon molding.

Example 11 Immediately after molding, a Keithley voltmeter reading of about 1.5 volts was noted. The control specimen showed a voltmeter reading of over 20 volts.

The results were Example 12 60 grams. of" septahyd'roxypropylated; diethylene triamine dissolved in 60 grams of water, were. incorporated into 666- grams of polystyrene emulsion con; tainingv 30% polystyrene solids.

760 grams of granulated polystyrene were placed. in. a. a Baker-Perkins mixer. With the mixer in operation, the polystyrene emulsion additive mixture was slowly added. The resultant slurry was then dried at 65 C. for 48 hours at which time it was found to be water-free. The resultant mixture which contained 6% of the addit-ive; when molded! as in Example 1, yieldedmoldings:

which when: tested as. in: Example 1., exhibitedsdestatic'izedi characteristics: similar to the modified product of Example 1.

Example 13 p 40 grams of pentahydroxyethylated diethylene triarnii'ie dissolved in 40 grams of water was added to 400, grams of a 30% solids polystyrene emulsion. This mixture was spray dried and gave a free flowing, polystyrene powder containing 1 part of the additive to 3' parts of. The resultant concentrate was tumbled with 820 grams of a granulated polystyrene. The resultant blend was injection molded under conventional. polystyrene moldingconditions and yielded d'estatioizedmoldings having, properties comparable to that produced by the procedures of Example 1.

Example 14 24" grams" of a,aazodiisobutyronitrile was dissolvedin' 960 grams of monomeric styrene, 40! grams of penta- 1"00 grams.0f' the styrene and set aside. 860 grams of the styrene were placed in? a heated agitated reaction kettle into which nitrogen was bubbled. The styrene solution was heated" at 70 C. for 1 /2 hours until an exothermic reaction took place. The reaction was continued for an additional 30 minutes with the temperature 'being gradually increased to C. until considerable polymerization took place as evidencedby an increase in viscosity. The styrene additive mixture was then added to the solution in the reaction kettle. The mixture was transferred 1 to air-free containers whichwcre then sealed. The containers were maintained at a temperature of 90 C. for 48 hours. The resultant polymer was injection molded under normal polystyrene molding conditions. Moldings were clear and appeared equivalent to conventional polystyrene, except that when rubbed with a wool cloth, they would not become electrostatically charged as does unmodified polystyrene when so rubbed.

Example 15 2.0 grams of a,aazodiisobutyronitrile was dissolved in 800 grams of monomeric styrene along with 200 grams of pentahydroxyethylated diethylene triamine. The solu tion was placed in a heated agitated reaction kettle into which nitrogen was bubbled. The suspension was heated at 70 C. for 1 /2 hours until an exothermic reaction took place. The reaction was continued for an additional 30 minutes with the temperature being gradually increased to 90 C. Considerable polymerization took place as evidenced by an increase in viscosity. The mixture was transferred to air-free containers which were then sealed. The containers were held at 90 C. for 48 hours. The resultant polymer was extruded and chopped into granules. Later, 200 grams of the resulting granules were mixed with 800 grams of untreated polystyrene granules, extruded, chopped and injection molded under normal polystyrene molding conditions. were similar in quality to those made in Example 1.

For the purpose of illustrating the invention, examples have been shown of the application of our invention to plastic alloys of polystyrene, polyethylene, polyvinylohloride and polymethylmethacrylate and their copolymers.

The resulting moldings We wish it to be understood that the invention likewise may be utilized in treating other polymers such as polyacrylonitrile, polyfluoroethylene, polytrifluo'romonochlorm ethylene, polybutadienes, halogenated polystyrenes and mixtures and copolymers of these materials.

The term vinylidene as used herein is intended to define monomers containing a polymerizable unsaturated structure and is generic to vinyl and vinylidene monomers. Each of the polymers specifically exemplified in the preceding examples, namely: polystyrene, polymethylmethacrylate, polyvinyl chloride and polyethylene is a polymer of a vinylidene monomer, so defined.

By plastic alloy as used herein, we intend to encompass compositions comprising two or more types of polymeric molecules whether prepared by copolymerization or by intimate mixing. v Mixtures of the va 'ous additives may be employed providing the total amount is within the disclosed proportions for a single specie.

While we have disclosed what is at present considered the best mode for carrying out our invention, we apprec'iate. that it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention and it is, therefore, aimed in the appended claims to cover all such changes and modifications as fall within the true spirit ands'cope of the invention.

What we claimvis:

- 1'. A' composition of matter comprising a linear polymer of a vinylidene monomer, and adestaticizing agent consisting of from 1 to 50% tion of a compound from the group consisting of hydroxyalkylated polyethylene polyamines represented by the formula V wherein n is an integer from 2 to 4 and R, R R and by weight of the compose R are hydroxyalkyl groups having from 2 to 8 carbon atoms and the ammonium salts of said compounds. i 2. The composition of claim' 1 wherein said polymer is polystyrene. 3. The composition of claim l wherein polymer is polyvinyl chloride.

4. The composition of claim l'wherein polymer is polymethylmethacrylate. V

5. The composition of claim 1 wherein polymer is polyethylene. v

6. The composition of claim 1 wherein said linear polymer is a mixture of polymers from the group consisting of polyacrylonitrile, polystyrene and polybutadiene; 7. The'composition of matter of claim 1 wherein the destaticizing agent comprises from 1% to 7% by weight of the composition. 1

said linear said linear said linear.

8. The composition of claiml wherein said hydroxyr alkylated polyethylene polyamine is pentahydroxyalkyl! ated diethylene triamine.

9. The composition of claim 8 wherein said hydroxyalkylated polyethylene polyamine is pentalhydroxyethylated diethylene triamine.

10. The composition of claim 9 wherein said hydroxypentahydroxypropylalkylated polyethylene polyamine is ated diethylene triamine.

11. The composition of claim 9 wherein said hydroxyalkylated polyethylene polyamine is pentahydroxybutylated diethylene triamine.

12. The composition of claim 1 wherein said hydroxy alkylated polyethylene polyamine is hexahydroxyalkylatedtriethylene tetramine.

'13. The composition of'claim 1 wherein said hydroxyalkylated polyethylene polyamine is septahydroxya1kylated tetraethylene pentamine. j p

14. A composition of matter comprising an emulsion of polystyrene and between 1% and by weight, of a hydroxyalkylated polyethylene polyamine containing from 2 to 4 ethylene radicals in the polyethylenegroup and from 2 to 8 carbon atoms in the hydroxyalkylgroup. 15. The composition of claim 1 wherein said destaticiz ing agent is characterized by a vapor pressure of less than 760mm.at225 C.

No references cited. 

1. A COMPOSITION OF MATTER COMPRISING A LINEAR POLYMER OF A VINYLIDENE MONOMER, AND A DESTATICIZING AGENT COMSISTING OF FROM 1 TO 50% BY WEIGHT OF THE COMPOSITION OF A COMPOUND FROM THE GROUP CONSISTING OF HGYDROXYALKYLATED POLYETHYLENE POLYAMINES REPRESENTED BY THE FORMULA 